PRECURSORS FOR SILICON DIOXIDE GAP FILL
A full fill trench structure is described, including a microelectronic device substrate having a high aspect ratio trench therein and filled with silicon dioxide of a substantially void-free character and substantially uniform density throughout its bulk mass. A method of manufacturing a semiconductor product also is described, involving use of specific silicon precursor compositions for forming substantially void-free and substantially uniform density silicon dioxide material in the trench. The precursor fill composition may include silicon and germanium, to produce a microelectronic device structure including a GeO 2 /SiO 2 trench fill material. A suppressor component may be employed in the precursor fill composition, to eliminate or minimize seam formation in the cured trench fill material.
1 . A full fill trench structure comprising a microelectronic device substrate having a high aspect ratio trench therein and a full filled mass of silicon dioxide in said trench, said silicon dioxide being of a substantially void-free character and having a substantially uniform density throughout its bulk mass, as formed by full fill of the trench with a silicon dioxide precursor composition, and hydrolysis and condensation chemical reactions of the precursor composition to form the silicon dioxide full filled mass in the trench.
2 . The full fill trench structure of claim 1 , wherein said precursor composition comprises a precursor silicon compound selected from the group consisting of:
(i) aminosilanes of the formula (R 1 R 2 N) 4-x SiR x , wherein x is an integer having a value in a range of from 0 to 3, and each R, R 1 , and R 2 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(ii) alkoxysilanes of the formula (RO) 4-x SiR 1 x , wherein x is an integer having a value in a range of from 0 to 3, and each R and R 1 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(iii) alkoxydisilanes of the formula (RO) 3-x R 1 x Si—Si(OR) 3-x R 1 x , wherein x is an integer having a value in a range of from 0 to 2, and each R and R 1 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(iv) aminodisilanes of the formula (R 1 R 2 N) 3-x R x Si—Si(NR 1 R 2 ) 3-x R x , wherein x is an integer having a value in a range of from 0 to 2, and each R, R 1 , and R 2 is independently selected from among hydrogen, branched or unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(v) aminodisiloxanes of the formula (R 1 R 2 N) 3-x R x Si—O—Si(NR 1 R 2 ) 3-x R x , wherein x is an integer having a value in a range of from 0 to 2, and each R, R 1 , and R 2 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(vi) alkoxydisiloxanes of the formula (RO) 3-x R 1 x Si—O—Si(OR) 3-x R 1 x , wherein x is an integer having a value in a range of from 0 to 2, and each R and R 1 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(vii) aminodisilazanes of the formula (R 1 R 2 N) 3-x R x Si—NH—Si(NR 1 R 2 ) 3-x R x , wherein x is an integer having a value in a range of from 0 to 2, and each R, R 1 , and R 2 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(viii) alkoxydisilazanes of the formula (RO) 3-x R 1 x Si—NH—Si(OR) 3-x R 1 x , wherein x is an integer having a value in a range of from 0 to 2, and each R and R 1 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(ix) chloroaminosilanes of the formulae Cl 4-x Si(NR 1 R 2 ) x , wherein x is an integer having a value in a range of from 0 to 3, (R 1 R 2 N) 3-x Cl x Si—Si(NR 1 R 2 ) 3-x Cl x , wherein x is an integer having a value of 1 or 2, (R 1 R 2 N) 3-x Cl x Si—O—Si(NR 1 R 2 ) 3-x Cl x , wherein x is an integer having a value of 1 or 2, and (R 1 R 2 N) 3-x Cl x Si—NH—Si(NR 1 R 2 ) 3-x Cl x , wherein x is an integer having a value of from 1 or 2, and each R 1 and R 2 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(x) cyclosiloxanes and cyclosilazanes of the formulae:
wherein n is an integer having a value in the range of from 0 to 4, and each R 1 and R 2 is selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 6 -C 13 aryl, C 1 -C 6 dialkylamino, and C 1 -C 6 alkoxide;
(xi) linear polysiloxanes and polysilazanes;
(xii) silicon compounds of general formulae R 4-x SiL x wherein x is an integer having a value of from 1 to 3, and L 3-x R x Si—SiL 3-x R x wherein x is an integer having a value of from 0 to 2, L is selected from isocyanato (NCO), methylethylketoxime (R 1 R 2 C═N—O—), trifluoroacetate (CF 3 OCO), triflate (CF 3 SO 3 ), acyloxy (ROCO), β-diketonate (R 1 COCHCOR 2 ), β-diketiminate (R 1 CNR 2 CHCOR 3 ), β-diiminate (R 1 CNR 2 CHCNR 2 R 3 ), amidinate (RC(NR 1 ) 2 ), guanidinate {(R 1 R 2 N)C(NR 3 ) 2 }, alkylamino (NR 1 R 2 ), hydride, alkoxide (RO), and formato (HCOO) and each R, R 1 , R 2 , and R 3 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(xiii) oxiranylsilanes of the formulae
wherein x is an integer having a value in a range of from 0 to 3, n is an integer having a value in a range of 0 to 3, and each R 1 , R 2 , and R 3 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 6 -C 13 aryl, C 1 -C 6 alkylamino, and C 1 -C 6 alkoxide;
(xiv) silicon precursors containing ethylacetate groups, of the formula (ROCOCH 2 CH 2 ) x Si(OR 1 ) 4-x , wherein x is an integer having a value in a range of from 1 to 4, and each of R and R 1 is independently selected from among hydrogen, branched and unbranched C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, and C 6 -C 13 aryl;
(xv) (tBuHN) 2 (H 2 N)Si—Si(NH 2 )(NHtBu) 2 wherein tBu is tertiary butyl; and
(xvi) pre-polymer partial hydrolysis products of the foregoing compounds (i)-(xv).
3 . The full fill trench structure of claim 1 , wherein said silicon dioxide has been further processed for densification thereof after the hydrolysis and condensation chemical reactions.
4 . The full fill trench structure of claim 3 , wherein said densification is effected by exposure of the silicon dioxide to at least one of oxygen exposure, ultraviolet radiation, and low-temperature heating.
5 . The full fill trench structure of claim 2 , wherein said precursor silicon compound is hydrolyzed to a sol comprising Si(OH) 4 and said sol is condensed by condensation reaction in the presence of a condensing agent selected from the group consisting of ammonia, amines, disilanes, silicon tetrachloride, and chlorine-substituted compounds.
6 . The full fill trench structure of claim 2 , wherein said precursor silicon compound is hydrolyzed in exposure to at least one agent selected from the group consisting of moisture, water and protic solvents.
7 . The full fill trench structure of claim 2 , wherein said precursor silicon compound comprises aminosilane of the formula H 4-x Si(NR 2 ) x wherein x has the same integer value of from 1 to 3, and a chloroaminosilane is added to said aminosilane in a catalytically effective amount to catalyze condensation reaction of said aminosilane.
8 . The full fill trench structure of claim 7 , wherein said chloroaminosilane comprises Cl 4-x Si(NR 2 ) x , wherein x is an integer having a value in a range of from 1 to 3.
9 . The full fill trench structure of claim 8 , wherein said chloroaminosilane is added in an amount of from 0.05-5% weight percent, based on total weight of said chloroaminosilane and said aminosilane.
10 . The full fill trench structure of claim 2 , wherein said precursor silicon compound comprises an alkoxysilane, and a chloro-substituted silane or chloro-substituted disilane is added to said alkoxysilane in a catalytically effective amount to catalyze condensation reaction of said alkoxysilane.
11 . The full fill trench structure of claim 10 , wherein said chloro-substituted silane or chloro-substituted disilane is added in an amount of from 0.05-5% weight percent, based on total weight of said alkoxysilane and said chloro-substituted silane or chloro-substituted disilane.
12 . The full fill trench structure of claim 2 , wherein said precursor silicon compound comprises hexaethylaminodisilane.
13 . The full fill trench structure of claim 2 , wherein said precursor silicon compound comprises (tBuHN) 2 (H 2 N)Si—Si(NH 2 )(NHtBu) 2 .
14 . The full fill trench structure of claim 2 , wherein said precursor silicon compound comprises Si(NMe 2 ) 4 .
15 . The full fill trench structure of claim 1 , wherein the silicon dioxide precursor composition includes a composition selected from the group consisting of:
(a) precursor compositions of the formula (RO) 4-x SiH x , wherein x is an integer having a value of from 0 to 3;
(b) precursor compositions of the formula H 4-x Si(NR 2 ) x , wherein x is an integer having a value of from 1 to 4;
(c) precursor compositions of the formula H 4-x Si(NHR) x , wherein x is an integer having a value of from 1 to 4;
(d) precursor compositions of the formula (RO) 3-x H x Si—Si(OR) 3-x H x , wherein x is an integer having a value of from 0 to 2;
(e) precursor compositions of the formula (NR 1 R 2 ) 3-x H x Si—Si(NR 1 R 2 ) 3-x H x wherein x is an integer having a value in a range of from 0 to 2, and
each R, R 1 , R 2 is independently selected from among hydrogen, and branched and unbranched C 1 -C 6 alkyl.
16 . The full fill trench structure of claim 1 , wherein the silicon dioxide precursor composition includes a composition selected from the group consisting of silicon precursors in which the silicon atom is coordinated with ligands including at least one of isocyanato, methylethylketoxime, trifluoroacetate, triflate (F 3 SO 3 H), alkylamines, hydrides, alkoxides, disilanes, and formato.